Polyacrylate plastic compositions containing phenolic ether flame retardants

ABSTRACT

PLASTIC COMPOSITIONS CONTAINING POLYACRYLATES AND BISPHENOXY COMPOUNDS HAVING THE FORMULA :   (((A)I,(Z)M-PHENYL)-O-R-O-),(A)I&#39;&#39;,(Z)M&#39;&#39;-BENZENE   WHEREIN Z IS BROMINE OR CHLORINE, M ANDM&#39;&#39; ARE INTEGERS HAVING A VALVE OF 1-5, I AND I ARE INTEGERS HAVING A VALVE OF 0-2, R IS HEREIN DEFINED AND A IS CYANO, NITRO, LOWER ALKOXY, LOWER ALKYL, FLUORINE, DIALKYLAMINO, PHENYL, HALOPHENYL, BENZYL OR HALO-BENZYL.

United States Patent US. Cl. 260-453 R 14 Claims ABSTRACT OF THE DISCLOSURE Plastic compositions containing polyacrylates and bisphenoxy compounds having the formula:

wherein Z is bromine or chlorine, m and m are integers having a value of 1-5, i and i' are integers having a value of 0-2, R is herein defined and A is cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halophenyl, benzyl or halo-benzyl.

This application is a continuation-in-part of copending application Ser. No. 260,240, filed June 6, 1972 and now abandoned. The entire specification of this case, Ser. -No. 260,240, is to be considered as incorporated herein by reference.

The prior are considered in conjunction with the prep: aration of this application is as follows: US. 2,130,990; US. 2,186,367; US. 2,329,033; US. 3,666,692; US. 3,- 686,320; US. 3,658,634; German Pat. No. 1,139,636; German Pat. No. 2,054,522; Japanese Pat. No. (72) 14,500 as cited in vol. 77, Chemical Abstracts, col. l53737k (1972); Chemical Abstracts, vol. 13, col. 448 Chemical Abstracts, vol. 31, col. 7045 and Journal of the Chemical Society, pp. 2972-2976 (1963). All of these publications are to be considered as incorporated herein by reference.

The present invention relates to plastic compositions containing polyacrylates. More specifically, the present invention covers plastic compositions containing polyacrylates and certain bis-phenoxy compounds (hereinafter defined) as flame retardants for said plastic compositions.

'Polyacrylates and utility thereof are known in the art as exemplified by Acrylic Resins, M. B. Horn (Reinhold Plastics Applications Series), Reinhold Publishing Corporation, New York, 1960 and Encyclopedia of Polymer Science and Technology, vol. 1, pp. 246-328, John Wiley & Sons, Inc., New York, 1964 and which publications,

are in toto incorporated herein by reference.

The need for flame retarding polyacrylates has also been recognized in the art as exemplified by the two above-described publications and by U.S. 3,422,048 which is incorporated herein by reference.

The resultant disadvantages in the utilization of various prior art materials as flame retardants for polyacrylates include, without limitation, factors such as thermal migration, heat instability, light instability, non-biodegradable, toxicity, discoloration and the large amounts employed in order to be effective.

Thus, there is always a demand for a material which will function as flame retardant in polyacrylates and concurrently will not, by incorporation therein, adversely eifect the chemical and/or physical and/or mechanical properties of the resultant composition.

The prior art problem of providing a flame retarded invention is to provide polyacrylate compositions which are flarne retarded.

Another object of the present invention is to provide a material for polyacrylate compositions which will not substantially adversely elfect the chemical and/or physical and/or mechanical properties of said compositions.

A further object of the present invention is to provide a flame retardant which is economic and easy to incorporate into polyacrylate without being degraded or decomposed as a result of blending or processing operations.

It has been found that the foregoing objects can be obtained by the incorporation of a new class of bisphenoxy compounds in polyacrylate to subsequently provide flame retarded compositions which exhibit outstanding chemical, physical and mechanical properties.

The bis-phenoxy compounds used in the present invention composition have the formula:

(I) At zm isoaaoemzw In Formula I above, Z is bromine or chlorine, m and m are integers each independently having a value of 1-5; 1' and i are integers each independently having a value of 0-2; A is from the group, cyano (-CN), nitro (NO lower alkoxy (e.g. -OCH OC H lower alkyl (e.g. CH C H C H- C H fluorine, dialkylamino e.g. N(CH --N(C H phenyl (-C H halo-phenyl, benzyl (CH C H and halo-benzyl; and- R is from the group CHr-CH where S=saturated ring moom

( Al AP Patented May 14, 1974 TABLE IContinued Z mm the exemplary definitions of A, Z, R, i, i, m and m are listed in Table I.

. Compound No.

TABLE I 0 0 Sameasabove N Do Do In general, the bis-phenoxy compounds are prepared by reacting a halogenated phenol with a halogenated alkane at elevated temperatures in the presence of a basic material such as alkali metal hydroxides, carbonates, bicarbonates, oxides and hydrides. The preferred alkali metals are potassium and sodium. Where one desires to increase, for example, ease of handling the reaction mass, solvents such as ketones (e.g. acetone, methyl ethyl ketone, and methyl iso-butyl ketone), alcohols (e.g. methanol, ethanol, iso-propyl alcohol, butyl alcohol and glycols), or aqueous 7 solvents (e.g. water, a mi ture of Water and alcohol and a mixture of water and ketone) can be employed. The desired end product i.e. the bis-phenoxy compound, can be recovered from the reaction mass via various methods 0 CHzCH(OH)CHz. 3 Same as above. 1 1 1 1 1 1 1 1 l 1 1 1 1 2 0 1 2 1 1 2 1 1 (CH2) :0 (0112):. 1 CHzO CH2. 1 Same as above. 1 Do. 1 Do. 1 (CH2) to (CH1) 4. 1 OHzO CH2. 1 (CHzhO (0112):. 1 CHzOCHz. 1 Same as above. Do. (CHzhOCHz. CHzO CH2. (CH2) :0 (CH2) (EH20 CH2. Same as above.

Do. Do. Do.

1 CHz(CoH4) CH2.

CHKCgHBra) CH2. 1 CHflCaHzBrz) CH2. 1 CHKCGBH) CH2. 1 CHz(CeHBI3) CH:- 1 CHKCoHO CH2. 1 Same as above. 1 CHflCoHzBn) CH2. 1 ()HflCoHBn) CH2. 1 CHz(CaCl4) CH1. 1 CHz(CsH4) CH2.- 2 CHKCGHBIE) CH1. 0 CHz(CuH4) CH2- 1 CH2(C0B1'4) CH2. 2 CH2(CIH4) CH2. 1 Same as above. Do. Do. 1 CH2(CIB!4) CH2. 1 Same as above.

0 0 Same as above.

Do. Do Do. D Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do. Do.

CHaOCHz HzCoHaBH H m, i 0

-.............. 0 0 CH2CH(CH2OH)CH1.

CHzCaHg a a h Compound No.

such as distillation or crystalllzation Where the end prod- 75 not requires recovery via crystallization, various aromatic (II) (III) A; Av (ha-whe In the above reaction, X is halogen, preferably chlorine and R is the same as defined herein. Where m and m and i and z" are different integers, then equivalent molar portions of the particular halogenated phenol are used with equivalent portions of dissimilar halogenated phenol.

The above reaction is conducted at temperatures ranging from the freezing point of the initial reaction mass to the boiling point thereof. Preferably the temperatures are from about 40 C. to about 200 C. and more preferably from about 50 C. to about 175 C. It is to be understood that the reaction can be conducted under subatmospheric (e.g. i -V atmosphere), atmospheric or super-atmospheric (e.g. 1.5-10 atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.

The above-described processes can be carried out with conventional, readily available chemical processing equipment. For example, a conventional glass-lined vessel provided with heat transfer means, a reflux condenser and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in the examples set forth herein.

The amount of bis-phenoxy compound employed in the present invention compositions is any quantity which will effectively render the polyacrylate containing composition flame retardant. In general, the amount used is from about 1% to 25% by weight, based on the total weight of the composition. Preferably, the amount employed is from about 5% to about by weight. It is to be understood that any amount can be used as long as it does not substantially adversely eifect the chemical and/or physical and/or mechanical properties of the end polymer composition. The amount utilized, however, is such amount which achieves the objectives described herein.

It is to be understood that the terms polyacrylates as used herein means acrylic polymers including acrylic acid polymers and copolymers and acrylic ester polymers and copolymers. For example, there may be mentioned materials which contain one of the repeating units C H: -CH-CH- and -CH 000R (acrylate polymers) (methacrylate polymers) where R is an alkyl or aryl radical or (in water-soluble polymers) a monovalent cation.

Thus the polyacrylates used in the present invention compositions is any polyacrylates herein defined and which one so desires to flame retard. It is to be understood that the polyacrylates used can be a virgin material, i.e. sub stantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the polyacrylates can have additive (such as those mentioned and described can have additives (such as those mentioned and described with or after the addition of the bis-phenoxy compounds.

rAnother facet of the present invention relates to the use of certain metal compounds with the bis-phenoxy compounds to promote a cooperative elfect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These enhancing agents" are from the group antimony, arsenic, bismuth, tin and zinc-containing compounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBI'3, SbI AS203, AS205, 2111304, B3B204'H20, 2'ZnO-3B 0- -35H 'O and stannous oxide hydrate. The preferred enhancing agent is antimony trioxide.

The amount of enhancing agent employed in the present invention compositions is any amount which when used with said bis-phenoxy compounds will promote a cooperative eifect therebetween. In general, the amount employed is from about 1% to about 15%, preferably from about 2% to about 10%, by weight, based on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved.

It is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors; antioxidants; antistatic agents; antimicrobials; colorants; flame retardants such as those listed on pp. 456-458, Modern Plastics Encyclopedia, ibid. (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour); calcium carbonate (chalk, limestone, and precipitated calcium car bonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and. zinc); polymers (comminuted polymers and elastomerplastic blends); silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are

more fully described in Modern Plastics Encyclopedia, ibid., and which publication is incorporated herein (in toto) by reference. The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely effect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0% to about and specifically from about 1% to about 50%.

The bis-phenoxy compounds can be incorporated in to the polyacrylates at any processing stage in order to prepare the present invention compositions. In general, this s undertaken prior to fabrication either by physical blendmg or during the process of forming polyacrylates per se. Where one so desires, the bis-phenoxy compounds may be m cronized into finely divided] particles prior to incorporation into the polyacrylates.

EXAMPLE I A virgin polymethylmethacrylate plastic material (Lucite-180, a product of E. I. du Pont de Nemours and Company, Wilmington, Del., and being substantially free of additives) is utilized as the base resin in order to prepare 26 formulations (plastic compositions). With the exception of formulation No. 1, the particular bis-phenoxy (and the antimony trioxide enhancing agent where indi cated) is incorporated into the plastic by adding both to a Brabender mixer (Plastic-Corder, Torque Rheometer, Model PLV-lSO, C. W. Brabender Instruments Inc., South Hackensack, N.J.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.

The resultant mixture is heated to about 300 C.; at this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table II. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to compression molding in a Wabash press by placing said chips be tween two plantens, the bottom of which contains four equal size depressions three inches by five inches by M; inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said chips and thus provide solid samples (after cooling) for testing.

Portions of the samples of each respective formulation (Nos. 1-26) prepared according to the above described procedure are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D-2863-70. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and extinguishment. This procedure is fully set forth in Underwriters Laboratories bulletin entitled IUL 94, Standard for Safety, 1st ed., September 1972 and which is incorporated herein by reference. .ASTM No. D-2863-70 is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, 0.1., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of contmuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards-Part 27, published by the American Society for Testing and Materials, 1916 Race St., Philadelphia, Pa.; this publication is to be considered as incorporated in toto) herein by reference.

The results of these flammability tests are shown in Table II.

TABLE II.FLAMMABILITY DATA FOR POLYACRYLATE PLASTIC COMPOSITIONS CONTAINI COMPOUNDS NG BIS PHENOXY Bls-phenoxy Enhancing compound agent Oxygen Formulation $11203, index, UL No. No. Percent percent percent 94 0 20.0 SB 20 0 24.0 SB 20 32.5 SE-0 0 22.5 SB 20 10 30.0 SE-0 20 0 22.0 SB 20 10 29.5 SE-O 20 0 21.5 B 20 10 28.5 SE-l 20 0 22.5 SB 20 10 30.0 SE-O 20 0 23.0 SB 20 10 31.0 SE-O 20 0 24.5 SB 20 10 35.5 SE-O 20 0 22.5 SB 20 10 31.0 SE-O 20 0 22.5 SB 20 10 30.5 SE-O 20 0 21.5 SB 20 10 30.0 SE-0 20 0 22.0 SB 20 10 29.5 SE-l 20 0 23.5 SB 20 10 31.5 SE-O 20 10 32.0 SE-O Referring to Table II, the bis-phenoxy compound number relates to the structural formulae heretofore set forth in Table I; a difference of 2% in the Oxygen Index values is considered significant; and the -UL 94 values are'on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE0, SE-l, SE-2, SB and Burns.

The results shown in Table II demonstrate the unique effectiveness of these bis-phenoxy compound as flame retardants for polyacrylates. Specifically, formulation No. 1 (the control) had a 0.1. of 20.0 and UL 94 value of SB.

In the even numbered formulations, the use of the particular bis-phenoxy compound results in a significant increase in fire retardancy as measured by 01. (While these formulations also had a SB rating, UL 94, the individual UL rating has a wide range of values and thus the 0.1. number is, in this case, more indicative of increased flame retardancy.)

The use of an enhancing agent such as Sb O to promote a cooperative effect between such agent and the bisphenoxy compound is fully demonstrated via the results obtained from testing the odd numbered formulations. The highest UL '94 ratings and significantly higher 0.1. values are obtained when using an enhancing agent.

EXAMPLE II Example I is repeated twice; once using a 10% bisphenoxy compound level and 3% Sb O level and secondly, 15% and 5% levels respectively. At both levels, the 01. values and UL 94 ratings are slightly lower than the 20% level of Example I.

EXAMPLE III Portions of the solid samples of formulations Nos. l-26 prepared according to the above described procedure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:

(1) Tensile strength (at break):

(2) Flexural strength: ASTM Test No. D790-63;

(3) Flexural modulus: ASTM Test No. D79063;

(4) Notched Izod impact: ASTM Test No. 13256-56;

and

(5) Heat distortion temperature (HDT): ASTM Test No. D648-56.

Each of the aforementioned ASTM tests are standard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application. All of these ASTM tests are to be considered as incorporated herein by reference.

The results of these ASTM tests show that the physical properties of the present invention compositions are basically the same (except O1. and UL 94 values) as the plastic material without the flame retardant (i.e. formulation No. 1). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the novel compounds are incorporated therein.

EXAMPLE IV The procedure of Examples I, II and III are repeated except that the enhancing agent used is zinc borate in stead of Sb O Substantially the same results are obtained using zinc borate as those obtained using Sb O EXAMPLE V Strip samples of each of formulation Nos. 1 through 26, Table II, are subjected to light stability tests via the use of a Weather-Ometer, model 25/18 W.R., Atlas Electrical Devices Company, Chicago, Ill. Utilizing an operating temperature of F. and a 50% relative humidity, each strip is subjected to 200 hours of simulated daylight via the use of a carbon arc. The results show that after 200 hours, there is no significant discoloration in any strip tested and which demonstrates that the present invention compositions are highly resistant to deterioration by light.

EXAMPLE VI Samples of each of formulation Nos. 1 through 26 Table II, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a Thermal Balance, model TGS1, Perkin-Elmer Corporation, Norwalk, Conn., and an electrical balance, Cahn 2580 model, Cahn ASTM Test No.

Instrument Company, Paramount, Calif. The results of these tests show that the bis-phenoxy compound containing formulations had more than adequate stability for melt processing and subsequent heat aging (i.e. high temperature applications) and thus demonstrating that the particular bis-phenoxy are quite compatible with the plastic material. The bis-phenoxy compound stability thus aids in providing suflicient flame retardancy at the plastic decomposition temperature. This test also demonstrates that these compounds do not exhibit migration.

In view of the foregoing examples and remarks, it is seen that the plastic compositions, which incorporate these compounds, possess characteristics which have been unobtainable in the prior art. Thus, the use of these compounds in the above described plastic material as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionality of any particular material in any polymer system until it is actively undergone incorporation therein and the resultant plastic composition tested according to various ASTM Standards. Furthermore, it is necessary, in order to have commercial utility, that the resultant flame retarded plastic composition possess characteristics such as being non-toxic. Use of these compounds in the plastic material has accomplished all of these objectives.

The above examples have been described in the foregoing specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention.

What is claimed is:

1. A plastic composition containing polyacrylate having incorporated therein an effective amount of a flame retardant which is a compound having the formula:

wherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of 1-5; i and i are integers having a value of -2; A is selected from the group consisting of cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halophenyl, benzyl and halo-benzyl; and R is selected from the group consisting of m where S=saturated TLC- s on, ring 2. The composition as set forth in claim 1 wherein i and i' are both 0.

3. The composition as set forth in claim 1 wherein i and i' are both 1.

4. The composition as set forth in claim 1 wherein i and i are both 2.

5. The composition as set forth in claim 3 wherein Z is bromine and A is cyano.

6. The composition as set forth in claim 3 wherein Z is bromine and A is nitro.

7. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkoxy.

8. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkyl.

9. The composition as set forth in claim 3 wherein Z is bromine and A is fluorine.

10. The composition as set forth in claim 3 wherein Z is bromine and A is dialkylamino.

11. The composition as set forth in claim 3 wherein Z is bromine and A is phenyl.

12. The composition as set forth in claim 3 wherein Z is bromine and A is halo-phenyl.

13. The composition as set forth in claim 3 wherein is bromine and A is benzyl.

14. The composition as set forth in "claim 3 wherein Z is bromine and A is halo-benzyl.

References Cited UNITED STATES PATENTS 3,658,634 4/1972 Yanagi et al. 161-403 3,717,609 2/1973 Kutner 26045.95 G

MAURICE J. WELSH, JR., Primary Examiner U.S. C1. X.R'..

260-41 R, 41 A, 41 B, 41 C, 45.75 R, 45.95 G, 613 B, Dig. 24

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION P tent N 3.810.867 D t May 14, 1974 Inventor) Arnold L. Anderson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9, line 40 (which is the foorth line of Claim 1) which reads:

is amended to read:

Signed and sealed this 4th day of March 1.975.

(SEAL) Attest:

' C. MARSHALL DANN Commissioner of Patents and Trademarks RUTH C. MASON Attesting Officer FORM F'O OS? MD-62V 

